Laminated resin film having a metallic appearance

ABSTRACT

A laminated resin film having a metallic appearance comprises: 
     (a) a polyvinyl chloride type resin film having a total light transmission of at least 30% and a tensile strength at 5% elongation of not higher than 2 kg/cm; 
     (b) a thin polyurethane type resin layer laminated on one surface of the resin film and having a total light transmission of at least 30% and a tensile strength at 100% elongation within the range of 50 to 550 kg/cm; and 
     (c) a metal layer having a thickness of 50 to 2,000 Å formed and adhering onto the polyurethane type resin layer. The film is useful particularly as a marking film.

DESCRIPTION

1. Technical Field

The present invention relates to a laminated resin film having ametallic appearance and more particularly to a laminated resin filmhaving a metallic appearance which can impart a beautiful ornament of ametallic tone to a substrate by being affixed on to a desired substratewith an adhesive or a pressure-sensitive adhesive, or by means ofthermal lamination or the like.

2. Background Art

Hitherto, as the resin film having a metallic appearance (hereafter,sometimes referred to as a metallic tone film), there have been known,for example, those which are composed of a resin film, such as apolyester type film, an acrylic type film, a polyvinyl chloride typefilm or the like, on one surface of which is formed a thin metal layerby a process of deposition, sputtering or the like, and they are usedmainly for ornamental purposes and the like.

In the case of metallic tone films prepared using a polyester resin filmas the resin film, although generally bonding between the metal layerand the polyester film is relatively good, they have disadvantages thatthe polyester resin is unsuitable for exterior use since it has a poorweatherability, and the polyester resin film is very hard and hence ithas a poor ability to follow curved surfaces, resulting in that itcannot be affixed onto curved surfaces.

Also, in the case of metallic tone films prepared using an acrylic resinfilm, the acrylic resin has a special character that it has a tendencyof losing flexibility with an increased solvent resistance, and hence itis impossible to obtain therefrom metallic tone films which areexcellent in both printability (solvent resistance) and flexibility.

Further, in the case of metallic tone films for exterior use preparedusing a polyvinyl chloride type resin film, the films can be impartedwith weatherability, flexibility and solvent resistance by adjustingtheir formulation in various ways to modify the properties thereof.However, in this case, generally bonding to the metal layer is difficultto be obtained and for this reason there arises a problem that peelingoff of the metal layer occurs, especially when used in the open air, orsome other problem. In addition, when used in the open air, it happensthat the metal layer is corroded and deteriorated with hydrochloric acidwhich is formed because of deterioration of the polyvinyl chlorideresin, resulting in failure to give metallic tone films for exterior usehaving good weatherabilities under the present conditions.

On the other hand, there have been made several approaches for obviatingthe aforementioned defects involved in the use of the polyvinyl chloridetype resin films.

For example, Japanese Patent Application Laid-Open No. Sho-58-2627discloses a method of metal deposition for polyvinyl chloride resinarticles which comprises providing on a surface of a polyvinyl chlorideresin article a cured film layer of a cationically polymerizable resincomposition which cures by irradiation of an actinic radiation, andpracticing metal deposition on a surface of the film. Japanese PatentApplication Laid-Open No. Sho-5-140965 discloses a primer compositionfor metal vacuum deposition which contains an aminoalkylsilane and afilm-forming resin.

However, no consideration was made at all about weatherability in theabove-proposed method and composition because both of them were notdesigned for exterior use. Also, because no consideration was made aboutprintability, the metallic tone film prepared according to the aboveproposal has a defect that fine cracks occur in the metal layer when anink clearer or the like is printed on the surface resin layer and it isthen dried. Presumably, this occurs because the metal layer cannotcompletely follow the deformation of the resin layer due to heat or thelike when heated for drying.

Also, in the case where metallic tone films for exterior use arefabricated which have an intermediate binding layer between a surfaceresin layer and a metal layer, especially where a flexible resin is usedin the surface resin layer, the surface resin layer undergoes elongationor deformation due to tension or heat applied thereto or due to solventswhich adhere thereto during the procedures in which the intermediatebinding layer and the metal layer are bonded, resulting in theoccurrence of cracks in the metal layer or sometimes in the breakage ofthe surface resin layer. Therefore, there arises a problem that it isdifficult to fabricate metallic tone films for exterior use stably.

Accordingly, it is an object of the present invention to provide ametallic tone film based on a polyvinyl chloride type resin film whichhas an excellent integrity of the polyvinyl chloride type resin film andthe metal layer, suffers no corrosion and deterioration in the metallayer, exhibits a sufficient weatherability even when used for exterioruse, has a flexibility enough to be affixed onto curved surfaces,excellent in various performances such as solvent resistance, warm waterresistance, and chemical resistance, and enables various types ofbeautiful printing.

DISCLOSURE OF INVENTION

The present invention provides a laminated resin film having a metallicappearance, comprising:

(a) a polyvinyl chloride type resin film having a total lighttransmission of at least 30% and a tensile strength at 5% elongation ofnot higher than 2 kg/cm;

(b) a thin polyurethane type resin layer laminated on one surface of theresin film and having a total light transmission of at least 30% and atensile strength at 100% elongation within the range of 50 to 550 kg/cm;and

(c) a metal layer having a thickness of 50 to 2,000 Å formed andadhering onto the polyurethane type resin layer.

The present invention provides a laminated resin film having a metallicappearance, further comprising:

(d) an acrylic type resin layer on the metal layer of the laminatedresin film.

Hereafter, the laminated resin film of the present invention will beexplained in more detail.

Polyvinyl Chloride Type Resin Film (a)

When used as the base of the laminated resin film of the presentinvention and affixed to a substrate for ornamental use, the polyvinylchloride type resin film (a) serving as the surface resin layer musthave a transparency enough to transmit therethrough and enable one tosee the metallic luster feeling of the metal layer bonded through thepolyurethane type resin layer described later on; it has a total visiblelight transmission of at least 30%, preferably not lower than 40%, andmore preferably not lower than 50%.

Also, it is desirable that the polyvinyl chloride type resin film (a)have a flexibility enough to enable it to follow the surface of asubstrate to which it is affixed even when the surface is irregular, andtherefore the resin film (a) should have a tensile strength at 5%elongation within the range of no higher than 2 kg/cm, preferably 1.9 to0.2 kg/cm, and more preferably 1.8 to 0.4 kg/cm.

Further, the thickness of the polyvinyl chloride type resin film (a) isnot limited strictly but can be varied depending on the purpose forwhich the laminated resin film of the present invention is used. It isconvenient that the thickness is within the range of generally 20 to 200microns, preferably 25 to 170 microns, and more preferably 30 to 150microns.

The polyvinyl chloride type resin used for forming the resin film (a)having the aforementioned characteristics includes homopolymers of vinylchloride or copolymers composed of vinyl chloride as a main componentand one or more other monomers copolymerizable therewith, having amolecular weight within the range of about 300 to about 3,000,preferably about 350 to about 2,500, and more preferably about 400 toabout 2,000, to which a plasticizer, one or more other resins formodification, and the like are optionally blended so that theaforementioned physical properties can be satisfied.

As the monomer copolymerizable with vinyl chloride, there can be citedolefin type monomers such as, for example, ethylene, propylene,butylene, isobutylene, etc.; dienes and vinylacetylene derivatives suchas, for example, butadiene, chlorobutadiene, pentadiene; halogenatedvinyl monomers such as, for example, vinyl fluoride, vinylidenechloride, vinyl bromide, etc.; (meth)acrylic acid ester monomers suchas, for example, ethyl acrylate, butyl acrylate, 2-hydroxyethylacrylate, 2-ethylhexyl acrylate, methyl methacrylate, butylmethacrylate, butyl methacrylate, propyl methacrylate, ethylene glycoldimethacrylate, etc.; vinyl ester monomers such as, for example, vinylacetate, vinyl chloroacetate, vinyl propionate, vinyl laurate, etc.;vinyl ether monomers such as, for example, methyl vinyl ether, propylvinyl ether, butyl vinyl ether, phenyl vinyl ether, allyl vinyl ether,etc.; styrene, methylstyrene, dimethylstyrene, vinylstyrene,chlorostyrene, vinylphenol, etc. They may be used singly or two or moreof them may be used in combination. It is preferred that in thecopolymer, vinyl chloride occupies at least 70% by mole, preferably notless than 80% by mole, and more preferably not less than 90% by mole,and the remainder is the aforementioned copolymerizable monomer.

As the plasticizer which can be blended, there can be used also thosewhich are usually used in polyvinyl chloride resins. There can be cited,for example, liquid polyester type plasticizers derived from a C₄ -C₁₅dibasic acid and a C₂ -C₂₀ dihydric alcohol. Specific examples of such aliquid polyester type plasticizer include liquid polyester plasticizersobtained by reacting one to three kinds of dibasic acids selected fromamong C₄ -C₁₅ dibasic acids such as maleic acid, adipic acid, phthalicacid, azelaic acid, sebacic acid, etc. with one to five kinds ofdihydric alcohols selected from among C₂ -C₂₀ dihydric alcohols such asethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, neopentylglycol, dipropyl glycol, 1,6-hexanediol,2,2,4-trimethyl-1,3-pentanediol, 1,5-pentanediol, etc., and a chainstopper properly selected from, for example, acetic acid, coconut oilfatty acid, n-octyl alcohol, and n-decyl alcohol. Such liquid polyesterplasticizers may be used singly or two or more of them may be used incombination.

Examples of other plasticizers for vinyl chloride resins includephthalic acid derivatives, for example, dimethyl phthalate, diethylphathalate, dibutyl phthalate, di-(2-ethylhexyl)phthalate, di-n-octylphthalate, higher alcohol phthalates, diisooctyl phthalate, diisobutylphthalate, dipentyl phthalate, diisodecyl phthalate, ditridecylphthalate, diundecyl phthalate, di-(heptylnonylundecyl) phthalate,benzyl phthalate, butylbenzyl phthalate, dinoyl phthalate, di-n-alkylphthalates, di-n-isoalkyl phthalates, etc.; isophthalic acidderivatives, for example, dimethyl isophthalate, di(2-ethylhexyl)isophthalate, diisooctyl isophthalate, etc.; tetrahydrophthalic acidderivatives, for example, di-(2-ethylhexyl) tetrahydrophthalate,di-n-octyl tetrahydrophthalate, diisodecyl tetrahydrophthalate, C₇ -C₁₀alkyl tetrahydrophthalate, etc.; adipic acid derivatives, for example,di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate,benzyloctyl adipate, di-(butoxyethoxyethyl) adipate; azelaic acidderivatives, for example, di-(2-ethylhexyl)azelate, diisooctyl acelate,di-2-ethylhexyl 4-thioazelate; sebacic acid derivatives, for example,di-n-butyl sebacate, di(2-ethylhexyl) sebacate, etc.; maleic acidderivatives, for example, di-n-butyl maleate, dimethyl maleate, diethylmaleate, etc.; fumaric acid derivatives, for example, di-n-butylfumarate, di-(2-ethylhexyl) fumarate, etc.; trimellitic acidderivatives, for example, tri-(2-ethylhexyl) trimellitate, tri-n-octyltrimellitate, triisodecyl trimellitate, etc.; citric acid derivatives,for example, triethyl citrate, tri-n-butyl citrate, acetyl triethylcitrate, etc., itaconic acid derivatives, for example, monomethylitaconate, monobutyl itaconate, dimethyl itaconate, etc.; oleic acidderivatives, for example, butyl oleate, tetrahydrofurfuryl oleate,glyceryl monooleate, etc.; ricinolic acid derivatives, for example,methyl acetyl acetyl ricinolate, butyl acetyl ricinolate, glycerylmonoricinolate, etc.; stearic acid derivatives, for example, n-butylstearate, glyceryl monostearate, diethylene glycol distearate, etc.; inaddition, diethylene glycol monolaurate, benzenesulfone butyramide,trimethyl phosphate, tributoxyethyl phosphate, tetra-2-ethylhexylpyromellitate, diethylene glycol dibenzoate, glycerol monoacetatechlorinated paraffin, epoxy derivatives having an oxirane oxygen contentof 2 to 9% and a molecular weight of no higher than 1,000, etc. They canbe used in an amount within the range of generally 1 to 100% by weight,preferably 1.5 to 70% by weight, and more preferably 20 to 50% by weightbased on total weight of the polyvinyl chloride type resin.

Further, as the resin for modification there can be cited, for example,ethylene/vinyl ester type resins, acrylic type resins, urethane typeresins, polyester type resins, etc. These may be used in an amountwithin the range of generally 0.1 to 70% by weight, preferably 0.5 to60% by weight, and more preferably 1 to 50% by weight based on totalweight of the polyvinyl chloride type resin.

The polyvinyl chloride type resin may if desired be blended with anyadditive known per se and usually used for polyvinyl chloride resins,for example, stabilizers such as, for example, calcium zinc typestabilizer (CZ-19J, produced by Katsuta Kako Co., Ltd.), tin typestabilizer (181 FSJ, produced by Katsuta Kako Co., Ltd.), barium zinctype stabilizer (BZ51J, produced by Katsuta Kako Co., Ltd.), and leadstearate type stabilizer (Pb-St, produced by Kosei Co., Ltd.);antioxidants such as, for example, monophenol type antioxidant (YoshinoxBHT, produced by Yoshitomi Pharmaceutical Co., Ltd.), amine typeantioxidant (Yoshinox EQ, produced by Yoshitomi Pharmaceutical Co.,Ltd.), and polyphenol type antioxidant (Ilganox 1010, produced byCiba-Geigy); lubricants such as, for example, hydrocarbon type lubricant(Ac-6A, produced by Allied Chemical), fatty acid type lubricant (F-3,produced by Kawaken Fine Chemicals), fatty acid ester type lubricant(Hoechst waxoop, produced by Hoechst Japan), and aliphatic alcohol typelubricant (Alcohol 86, produced by Kao Soap); for example, phthalic acidtype plasticizer (DOP, produced by Sanken Kako Co., Ltd.); ultravioletlight absorbents such as, for example, benzotriazole type ultravioletlight absorbent (Tinubin P, Tinubin 326, 327, produced by Ciba-Geigy),and hydroxybenzophenone type ultraviolet light absorbent (Cyasoap UV-9,produced by American Cyanamide) in amounts usually used.

As the polyvinyl chloride type resin which can be used suitably in thepresent invention, there can be cited, a semi-hard polyvinyl chlorideresin composition disclosed in Japanese Patent Application Laid-Open No.Sho-60-195146, having a stress at yield within the range of 1 to 6kg./cm² and having the following composition:

(A) 100 parts by weight of a polyvinyl chloride which may contain nomore than 20% by weight of a copolymerization component;

(B) 1 to 20 parts by weight of a liquid polyester type plasticizerhaving a number average molecular weight (Mn) of no lower than 1,500 and0 to 10 parts by weight of another plasticizer for polyvinyl chlorideresins; and

(C) 5 to 20 parts by weight of an ethylene/vinyl ester copolymer; and

a semi-hard polyvinyl chloride resin composition disclosed in JapanesePatent Publication No. Sho-63-24619 (U.S. Pat. No. 4,670,490specification), having a stress at yield within the range of 1 to 5kg/cm² and having the following composition:

(A) 100 parts by weight of a polyvinyl chloride which may contain nomore than 20% by weight of a copolymerization component;

(B) 10 to 80 parts by weight of a liquid polyester type plasticizerhaving a number average molecular weight (Mn) of no lower than 1,500 and0 to 10 parts by weight of another plasticizer for polyvinyl chlorideresins; and

(C) a low molecular weight (meth)acrylic type resin having a numberaverage molecular weight (Mn) within the range of 1,500 to 5,000 andbeing solid at 23° C. in an amount of 0.2 to 200% by weight based ontotal amount of the aforementioned plasticizers (B).

As more preferred polyvinyl chloride type resin which can be used in thepresent invention, there can be cited a semi-hard polyvinyl chlorideresin composition disclosed in Japanese Patent Application Laid-Open No.Sho-60-195147, having a stress at yield within the range of 1 to 6kg./cm², preferably 1 to 5 kg/cm², and more preferably 1.2 to 4.5kg./cm², and having the following composition:

(A) 100 parts by weight of polyvinyl chloride which may contain no morethan about 20% by weight of a copolymerization component;

(B) 1 to 20 parts by weight of a liquid polyester type plasticizerhaving a number average molecular weight (Mn) of no lower than 1,500 and0 to 10 parts by weight of other plasticizer for polyvinyl chlorideresins; and

(C) ethylene/vinyl ester of a saturated carboxylic acid/carbon monoxidetype copolymer in an amount of 45 to 350% by weight based on totalamount of the aforementioned plasticizers (B).

Hereafter, the preferred semi-hard polyvinyl chloride resin compositionwill be described in more detail.

No particular limitation is posed on the polyvinyl chloride (A) used inthe aforementioned semi-hard polyvinyl chloride resin composition andany polyvinyl chloride resin that has hitherto been used for molding canbe used. For example, there can be exemplified a polyvinyl chloridehaving a degree of polymerization of about 600 to about 3,000,preferably about 700 to about 2,000, more preferably about 800 to about1,800, and particularly preferably about 1,200 to about 1,600.

Further, the aforementioned polyvinyl chloride (A) may be a homopolymerof vinyl chloride or a copolymer containing up to about 20% by weight,preferably up to about 10% by weight, particularly preferably up toabout 6% by weight, of a copolymerization component. Examples of such acopolymerization component include vinyl monomers, for example, olefintype monomers such as, for example, ethylene, propylene, butylene,isobutylene, etc.; dienes such as, for example, butadiene,chlorobutadiene, pentadiene, etc. and vinylacetylene derivatives;halogenated vinyl monomers such as, for example, vinyl fluoride,vinylidene chloride vinyl bromide, etc.; (meth)acrylic acid estermonomers such as, for example, ethyl acrylate, butyl acrylate,2-hydroxyethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate,butyl methacrylate, butyl methacrylate, propyl methacrylate, ethyleneglycol dimethacrylate, etc.; vinyl ester monomers such as, for example,vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl laurate,etc.; vinyl ether monomers such as, for example, methyl vinyl ether,propyl vinyl ether, butyl vinyl ether, phenyl vinyl ether, allyl vinylether, etc.; styrene derivatives such as,,for example, styrene,methyl-styrene, dimethylstyrene, vinylstyrene, chlorostyrene,vinylphenol, etc.

The polyvinyl chloride as described above can be prepared by a knownmethod or commercially available. For example, there can be cited, forexample, commercially available vinyl chloride resins such as Zeon 121,Zeon 131, Zeon 25, Zeon 135J (vinyl chloride resins, products by NipponZeon Co., Ltd.), Vinica P-440, Vinica P-400 (vinyl chloride resins,products by Mitsubishi Monsanto Co., Ltd.), Sumilit PX (vinyl chlorideresin, product by Sumitomo Chemical Co., Ltd.) and the like.

The plasticizers (B) which can be used in the aforementioned semi-hardpolyvinyl chloride resin composition comprise 5 to 70 parts by weight,preferably 10 to 60 parts by weight, and more preferably 20 to 50 partsby weight of, a polyester type plasticizer having a number averagemolecular weight of no lower than about 1,500, preferably about 1,500 toabout 6,000, more preferably about 1,500 to about 4,000, and morepreferably about 2,000 to about 4,000, and 0 to 10 parts by weight,preferably 2 to 8 parts by weight, and more preferably 3 to 7 parts byweight of other plasticizer for vinyl chloride resins. The parts byweight for the aforementioned plasticizers are based on 100 parts byweight of the aforementioned polyvinyl chloride.

As the liquid polyester type plasticizer, there can be cited, forexample, liquid polyester plasticizers obtained by reacting one to threekinds of dibasic acids selected from among C₄ -C₁₅ dibasic acids such asmaleic acid, adipic acid, phthalic acid, azelaic acid, sebacic acid,etc. with one to five kinds of dihydric alcohols selected from among C₂-C₂₀ dihydric alcohols such as ethylene glycol, 1,2-propylene glycol,1,3-butylene glycol, neopentyl glycol, dipropyl glycol, 1,6-hexanediol,2,2,4-trimethyl-1,3-pentanediol, 1,5-pentanediol, etc., and a chainstopper properly selected from, for example, acetic acid, coconut oilfatty acid, n-octyl alcohol, and n-decyl alcohol. By the term "liquid"in the expression "liquid polyester plasticizer" is meant a viscousliquid having a viscosity at 25° C. of 500,000 poises or less asmeasured with a BH type rotational viscometer, and the number averagemolecular weights of the polyester type plasticizers (Mn) are valuesmeasured by GPC (Gel Permeation Chromatography) method and converted.

Such polyester type plasticizers are available as products on themarket. There can be cited, for example, PN-150, PN-260, PN-446(polyester type plasticizers, product by Adeka Argus Chemical Co.,Ltd.), NS-3700 (polyester type plasticizer, product by Dainippon SeikaKogyo Co., Ltd.), P-204N, P-29 (polyester type plasticizers, products byDai-Nippon Ink and Chemicals Co., Ltd.), G-25, G-40 (polyester typeplasticizers, products by Rohm & Haas Co.), SP-171, DIDA, SP-501,SP-115S (polyester type plasticizers, products by Sanken Kako Co.,Ltd.), Kodaflex NP-10 (polyester type plasticizer, product by EastmanChemical Products Co.), Flexol P-2H (polyester type plasticizer, productby Union Carbide Corp.), Edenol 1200 (polyester type plasticizer,product by Henkel Co.), Rheoplex 100, Rheoplex 110, Rheoplex 220(polyester type plasticizers, products by Ciba-Geigy), etc. Thesepolyester type plasticizers may be used singly or two or more of themmay be used in combination.

In the aforementioned composition, a small amount, e.g., up to about 10parts by weight, preferably up to about 5 parts by weight, per 100 partsof the polyvinyl chloride, of other plasticizer for vinyl chlorideresins may be used in combination. Examples of such other plasticizerfor vinyl chloride resins include the following plasticizers: phthalicacid derivatives, for example, dimethyl phthalate, diethyl phthalate,dibutyl phthalate di-(2-ethylhexyl)phthalate, di-n-octyl phthalate,higher alcohol phthalates, diisooctyl phthalate, diisobutyl phthalate,dipentyl phthalate, diisodecyl phthalate ditridecyl phthalate, diundecylphthalate, di(heptylnonylundecyl) phthalate, benzyl phthalate,butylbenzyl phthalate, dinonyl phthpalate, di-n-alkyl phthalates,di-n-isoalkyl phthalates, etc.; isophthalic acid derivatives, forexample, dimethyl isophthalate, di-(2-ethylhexyl) isophthalate,diisooctyl isophthalate, etc.; tetrahydrophthalic acid derivatives, forexample, di-(2-ethylhexyl) tetrahydrophthalate, di-n-octyltetrahydrophthalate, diisodecyl tetrahydrophthalate, C₇ -C₁₀ alkyltetrahydrophthalate, etc.; adipic acid derivatives, for example,di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate,benzyloctyl adipate, di-(butoxyethoxyethyl) adipate; azelaic acidderivatives, for example, di-(2-ethylhexyl)azelate, diisooctyl azelate,di-2-ethylhexyl 4-thioazelate; sebacic acid derivatives, for example,di-n-butyl sebacate, di(2-ethylhexyl) sebacate, etc.; maleic acidderivatives, for example, di-n-butyl maleate, dimethyl maleate, diethylmaleate, etc.; fumaric acid derivatives, for example, di-n-butylfumarate, di-(2-ethylhexyl) fumarate, etc.; trimellitic acidderivatives, for example, tri-(2-ethylhexyl) trimellitate, tri-n-octyltrimellitate, triisodecyl trimellitate, etc.; citric acid derivatives,for example, triethyl citrate, tri-n-butyl citrate, acetyl triethylcitrate, etc., itaconic acid derivatives, for example, monomethylitaconate, monobutyl itaconate, dimethyl itaconate, etc.; oleic acidderivatives, for example, butyl oleate, tetrahydrofurfuryl oleate,glyceryl monooleate, etc.; ricinolic acid derivatives, for example,methyl acetyl acetyl ricinolate, butyl acetyl ricinolate, glycerylmonoricinolate, etc.; stearic acid derivatives, for example, n-butylstearate, glyceryl monostearate, diethylene glycol distearate, etc.; inaddition, diethylene glycol monolaurate, benzenesulfone butyramide,trimethyl phosphate, tributoxyethyl phosphate, tetra-2-ethylhexylpyromellitate, diethylene glycol dibenzoate, glycerol monoacetatechlorinated paraffin, epoxy derivatives having an oxirane oxygen contentof 2 to 9% and a molecular weight of no higher than 1,000, etc.

In the aforementioned semi-hard polyvinyl chloride resin composition,ethylene/vinyl ester of a saturated carboxylic acid/carbon monoxide typecopolymer (C) in an amount of 45 to 350% by weight, preferably 50 to300% by weight, and more preferably 55 to 250% by weight, based on totalamount of the plasticizers (B), is used together with the polyvinylchloride (A) and the plasticizers (B).

As the vinyl ester of a saturated carboxylic acid which constitutes theaforementioned copolymer, there can be cited, for example, vinyl estersof saturated aliphatic monocarboxylic acids, e.g., vinyl acetate, vinylpropionate, vinyl butyrate, vinyl versatate, vinyl stearate, etc. Amongthem, preferred is vinyl acetate.

Proportion of monomers in the copolymer is not limited strictly but maybe within the range of 1 to 20% by weight, preferably 2 to 10% byweight, and more preferably 2 to 6% by weight, of ethylene: 1 to 20% byweight, preferably 2 to 10% by weight, and more preferably 2 to 6% byweight, of vinyl ester of a saturated carboxylic acid : 1 to 20% byweight, more preferably 2 to 10% by weight, and more preferably 2 to 6%by weight, of carbon monoxide.

Such copolymers are themselves known per se, and can be prepared by themethod described in Japanese Patent Publication No. Sho-55-50063 (=U.S.Pat. No. 3,780,140 specification), and can have a number averagemolecular weight within the range of generally 600 to 3,000, preferably700 to 2,000, and more preferably 800 to 1,800. Marketed products, forexample, Zone 135J, Zeon 38J (produced by Nippon Zeon Co., Ltd.), etc.can be used.

Further, the aforementioned semi-hard polyvinyl chloride resincomposition may contain, if desired: (D) a low molecular weight acrylictype resin having a number average molecular weight of about 1,500 toabout 50,000, preferably about 2,000 to about 40,000, and morepreferably about 2,500 to about 30,000 and being solid at 23° C. in anamount within the range of up to 20% by weight, preferably about 5 toabout 15% by weight, and more preferably about 7 to about 12% by weightbased on the polyvinyl chloride (A).

Such a low molecular weight (meth)acrylic type resin can be readilyprepared by polymerizing at least one C₁ -C₁₈ alkyl ester of(meth)acrylic acid, if desired, together with one or more other monomerscopolymerizable therewith. It is desired that the (meth)acrylic typeresin have a glass transition temperature (Tg) of generally not lowerthan 30° C., preferably not lower than 35° C.

As the method for fabricating films using the polyvinyl chloride typeresin as described above, a method which is known per se can be used.For example, a film having a desired thickness can be fabricated bysubjecting a solution containing the resin component to casting filmforming means such as a cast method or a coater method using a supportfilm as a carrier. Examples of the solvent used on this occasion includetetrahydrofuran, methyl ethyl ketone, methylene chloride,dimethylformamide, alcohols, etc.

According to the above-explained fabricating method, the support filmserves as a carrier for fixing respective layers in the metallic tonefilm in each of the steps described later on and at the same time servesas a protective layer for the surface resin layer, making it possible tofabricate the aforementioned metallic tone film for exterior use withease and certainty and effectively prevent the surface from beingdamaged due to external factors in each step.

To note, in the aforementioned fabricating method, a step of forming oneor more other layers such as surface coating layer and the like can beadded, if required.

Polyurethane Type Resin Layer (b)

As the polyurethane type resin laminated on one surface of theaforementioned polyvinyl chloride type resin film (a), there is used onehaving a total visible light transmission of at least 30%, preferablynot lower than 40%, and more preferably not lower than 50%, and atensile strength at 100% elongation within the range of 50 to 550kg/cm², preferably 60 to 450 kg/cm², and more preferably 70 to 350kg/cm². Its kind is not limited strictly and can be selected from a widerange so far as the aforementioned conditions are met.

As the isocyanate component which can be used in the preparation of thepolyurethane resin that can be used in the present invention, there canbe employed aliphatic type, alicyclic type, aromatic type or their mixedtype polyisocyanate compounds may also be used. More specifically, therecan be cited, for example, so-called aromatic multifunctionalisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylenediisocyanate, p-phenylene diisocyanate, 4,4-diphenylmethanediisocyanate, naphthalene, 1,5-diisocyanate, tolidine diisocyanate,xylene diisocyanate, transcyclohexane 1,4-diisocyanate,tetramethylxylene diisocyanate, etc.; pentamethylene diisocyanate,hexamethylene diisocyanate, heptamethylene diisocyanate,4,4'-dicyclohexylbutane diisocyanate, lysine diisocyanate, isophoronediisocyanate, hydrogenated methylenediphenyl diisocyanate, hydrogenatedxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecanetriisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane,1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate,trimethylhexamethylene diisocyanate, etc.

Also, there can be cited dimers (uretidiones), trimers (isocyanurates),and modified products such as carbodiimide-modified products,allophanate-modified products, biuret-modified products, urea-modifiedproducts, and urethane-modified products, of the aforementionedisocyanate components, or blocked isocyanates thereof. These may be usedsingly or two or more of them may be used in combination. Particularly,pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylenediisocyanate, 4,4'-dicyclohexylmethane diisocyanate, lysine diisocynate,isophorone diisocyanate, hydrogenated methylenediphenyl diisocyanate,hydrogenated xylylene diisocyanate, lysine ester triisocyanate,1,6,11-undecane triisocyanate,1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-hexamethylenetriisocyanate, bicycloheptane triisocyanate, trimethylhexamethylenediisocyanate, etc., which are excellent in yellowing resistance, can beused favorably.

On the other hand, as for the polyol component, monomeric or polymericpolyols which have been generally used in the preparation ofpolyurethanes can also be used. There can be cited monomeric diols suchas, for example, ethylene glycol, propylene glycol, butane diol, hexanediol, cyclohexane dimethanol, diethylene glycol, dipropylene glycol,bisphenol, bishydroxyethoxybenzene, neopentyl glycol, triethyleneglycol, hydrogenated bisphenol A, etc.; polymeric polyols such as, forexample, polyester polyols, polycaprolactone polyols, polyether polyols,polycarbonate polyols, acrylic polyols, butadiene polyols, phenolicpolyols, epoxy polyols, etc. Specific examples of the polymeric polyolsinclude polyether diols prepared using water as an initiator, propyleneglycol, ethylene glycol, potassium hydroxide or alkylene oxide,polycarbonate diols prepared using 1,6-hexane diol, phosgene, ethylenecarbonate and 1,6-hexane diol, and polyethylene adipate prepared bycondensation with dehydration of adipic acid and ethylene glycol. Inaddition to such bifunctional alcohols, polyfunctional alcohols such as,for example, trimethylolethane, trimethylolpropane, pentaerythritol,glycerin, diglycerin, etc. can be used. Further, polyols having anethylenically unsaturated bond, for example, a polyester diolsynthesized using a polycarboxylic acid having an ethylenicallyunsaturated bond, e.g., maleic acid, itaconic acid or the like as a partof the carboxylic acid component may be used for the preparation ofpolyurethane resins having an ethylenically unsaturated bond.

The polyol component which can be used favorably in the presentinvention may include polyether polyols, polycarbonate polyols, acrylicpolyols, polyester polyols, etc.

The preparation of the polyurethane resin from the isocyanate componentand the polyol component as described above can be performed by a methodknown per se. For example, a method in which the components arepolymerized in a solvent for mixing such as dimethylformamide, methylethyl ketone or the like in polymerization tank by heating while mixingand stirring can generally be used, and objective resin can be obtainedby controlling the temperature, time, and the like.

Further, in the present invention, it is also possible to preparepolyurethane resins by preparing an isocyanate-terminated prepolymerfrom the aforementioned isocyanate and polyol components in advance, andthen reacting the prepolymer with a chain extender. As the chainextender which can be used here, there can be cited, for example,polyhydric alcohols such as ethylene glycol, 1,4-butylene glycol,2,3-butylene glycol, hydroquinone diethylol ether, etc.; diamines suchas ethylenediamine, propylenediamine, hexamethylenediamine, piperazine,isophoronediamine, cyclohexylmethanediamine,3,3-dichloro-4-,4'-diaminodiphenylmethane, diphenylmethaneamine,m-phenylenediamine, etc.; modified products of isocyanate such as dimerof tolylene diisocyanate, urea-modified product of isocyanate,urea-modified products of isocyanate, etc.; and the like. Here,trifunctional or more polyfunctional compounds play a role of acrosslinking agent too.

The polyurethane resin used in the present invention preferably has aweight average molecular weight within the range of generally 300 to200,000, preferably 1,000 to 150,000, and more preferably 5,000 to100,000. Hence, upon preparing the polyurethane resin, it is possible tocontrol the molecular weight using, if required, monoalcohols, such asmethanol, ethanol, propanol, etc.; monoamines, such as diethylamine,dipropylamine, dibutylamine, etc.; alkanolamines, such asmonoethanolamine, diethanolamine, monopropanolamine, dipropanolamine,etc. as a chain terminator.

Further, the aforementioned polyurethane resin may be modified bygraft-polymerizing therewith at least one vinyl monomer. As the vinylmonomer to be graft-polymerized, there can be cited, for example, C₁-C₁₂ alkyl esters of (meth)acrylic acid, such as methyl (meth)acrylate,ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate,pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate,octyl (meth)acrylate, nonyl (meth)acrylate, etc.; N-C₁ -C₆ alkyl(meth)acrylamide, such as methylol acrylamide, butylol acrylamide, etc.;C₂ -C₆ hydroxyalkyl esters of (meth)acrylate, such as hydroxyethyl(meth)acrylate, hydroxypropyl (meth)acrylate, etc., orcaprolactone-modified products thereof (for example, "Praxel FM Series",produced by Daicel Chemical Industry Co., Ltd.); polyalkylene glycolmono(meth)acrylate having a degree of polymerization within the range of2 to 50, such as triethylene glycol acrylate, diethylene glycolacrylate, poropylene glycol acrylate, hydroxypolyalkylene ether glycolmono(meth)acrylate, etc.; ethylenically unsaturated carboxylic acids,such as acrylic acid, methacrylic acid, maleic acid, itaconic acid,crotonic acid, etc.; oxyalkyl phosphate (meth)acrylate, such as ethyleneoxide phosphate (meth)acrylate, propylene oxide phosphate(meth)acrylate, etc.; dicyclopentenyl (meth)acrylate,N-vinylpyrrolidone, acrylonitrile, acrylamide, styrene, vinyltoluene,vinyl acetate, etc. These vinyl monomers may be used singly or two ormore of them may be used in combination.

Graft polymerization of these vinyl monomers to the polyurethane resincan be performed by a method known per se, for example, by allowing thepolyurethane resin and a monomer to coexist in the presence of acatalyst (azobisisobutyronitrile or the like) and react at a temperatureof about 80° C. for about 2 to 3 hours with heating under atmosphericpressure. The graft amount of the vinyl monomer may be varied dependingon the kind of the vinyl monomer, characteristics required for themodified polyurethane resin to be obtained and the like but is suitablewithin the range of generally up to 100% by weight, preferably 70 to 2%by weight, and more preferably 60 to 5% by weight.

As the polyurethane resin particularly preferred for forming thepolyurethane resin layer (b) of the present invention, there can becited, for example, a blend of a crosslinking graft polyurethane resinand an amino resin type crosslinking agent; the crosslinking graftpolyurethane resin can be prepared by graft polymerizing a vinyl monomermixture containing a hydroxyl group-containing vinyl monomer to apolyurethane resin which is prepared using as the polyol component anethylenically unsaturated bond-containing polyester diol synthesizedusing a polycarboxylic acid having an ethylenically unsaturated bond asa part of the carboxylic acid component, and containing on average 0.2to 3, preferably 0.4 to 2.5, and more preferably 0.5 to 2, ethylenicallyunsaturated bonds in the molecule and having a weight average molecularweight within the range of 300 to 200,000, preferably 1,000 to 150,000,and more preferably 5,000 to 100,000.

The aforementioned hydroxyl group-containing vinyl monomer includes theabove-described C₂ -C₆ hydroxyalkyl esters of the aforementioned(meth)acrylic acid or caprolactone-modified products thereof, andpolyalkylene glycol mono(meth)acrylates having a degree ofpolymerization within the range of 2 to 50, etc. They may be present inan amount within the range of generally 90 to 100% by mole, preferably80 to 20% by mole, and more preferably 70 to 30% by mole, based on totalamount of the vinyl monomer mixture.

It is preferred that the vinyl monomer mixture contain the carboxylgroup-containing ethylenically unsaturated monomer such as theaforementioned ethylenically unsaturated carboxylic acids in an amountwithin the range of generally 50 to 5% by mole, preferably 40 to 8% bymole, and more preferably 30 to 10% by mole, based on total amount ofthe vinyl monomer mixture from a point of view of increasingcompatibility with the crosslinking agent to form a uniform clear filmand the like.

The remainder of the vinyl monomer mixture may be at least one of theother vinyl monomers referred to hereinabove as the vinyl monomer to begrafted to the polyurethane resin.

It is suitable that these vinyl monomer mixtures be used in an amountwithin the range of generally no more than 150 parts by weight,preferably 100 to 1 part by weight, and more preferably 70 to 2 parts byweight, per 100 parts by weight of the polyurethane resin to which theyare to be grafted.

Grafting reaction of the aforementioned vinyl monomer mixture to thepolyurethane resin can be performed according to a graft polymerizationmethod known per se, for example, by subjecting a mixture of thepolyurethane resin and a vinyl monomer polymerization reaction in thepresence of a usual radical polymerization initiator such asazobisisobutyro-nitrile, benzoyl peroxide, di-tert-butyl peroxide,cumene hydroperoxide, etc., in an inert solvent according to thecircumstances.

On the other hand, as the amino resin type crosslinking agent which canbe blended with the crosslinking graft polyurethane resin thus prepared,there can be cited, for example, amino resin derivatives obtained bysubjecting the amino resin such as melamine resin, benzoguanamine resin,urea resin, etc. to methylolation, methoxylation, butoxylation or thelike.

While the compounding amount of the amino resin type crosslinking agentsmay be varied according to physical properties desired for thepolyurethane resin formed, it is convenient that the amino resin typecrosslinking agents are used in an amount within the range of usually 5to 60 parts by weight, preferably 7 to 50 parts by weight, and morepreferably 10 to 40 parts by weight.

The polyurethane resin may be blended with additives usually used in thetechnical field of coating composition, such as a dilution solvent foradjusting its viscosity (for example, dimethylformamide, methyl ethylketone, tetrahydrofuran, methylene chloride, alcohols, etc.), levelingagents (for example, dimethylpolysiloxane, fluorine-containingoligomers, acrylic oligomers, etc.), thixotropic agent (for example,polycarboxylic acid having a high degree of polymerization and saltsthereof, particulate silicon dioxide, particulate calcium carbonate,particulate organic bentonite, etc.), and the like. If required, thepolyurethane resin may contain catalysts for curing, colorants (dyes,general pigments, pearl pigments, metallic flakes, etc.), ultravioletlight absorbents, antioxidants, etc.

Further, in order to increase adhesion between adjacent layers, andimprove mechanical properties and chemical resistance, the polyurethaneresin may be blended with no more than 200 parts by weight, preferablyno more than 150 parts by weight, and more preferably no more than 100parts by weight, per 100 parts by weight of the polyurethane resin, ofone or more other resins having compatibility therewith, for example,phenol resins, furan resins, urea resins, melamine resins, guanamineresins, polyester type resins, epoxy resins, silicon resins, polyamidetype resins, polyvinyl chloride type resins, polyvinylidene chloridetype resins, vinyl acetate type resins, polyvinyl alcohols, polyvinylacetals, alkyd resins, styrene type resins, AS resins, ABS resins, AXSresins, (meth)acrylic resins, EVA resins, polyamide resins, cellulosederivatives, petroleum resins, etc.

The polyurethane type resins thus far described can be applied to onesurface of the aforementioned polyvinyl chloride type resin film (a) toform a polyurethane type resin film layer (b).

As the method for applying the polyurethane type resin on the polyvinylchloride type resin film (a), there can be cited, for example, a methodin which a solution of the aforementioned polyurethane type resin havinga suitable viscosity is prepared, and the solution is coated by usuallyused coating method such as spray coating, curtain flow coating, rollcoater coating, doctor knife coating, dip coating flow coating, brushcoating or the like.

While the thickness of the polyurethane type resin layer is not limitedstrictly, too small a thickness results in insufficient protection of ametal layer to be coated thereon, bonding, weatherability, etc. or onthe contrary too large a thickness is not only uneconomical but alsodecreases the flexibility of the laminated resin film obtained.Accordingly, it is suitable that the thickness of the polyurethane typeresin layer (b) be within the range of generally 0.5 to 50 microns,preferably 1 to 30 microns, and more preferably 2 to 20 microns.

In the case where the aforementioned crosslinking grafted urethane resinblended with an amino resin type crosslinking agent is used as thepolyurethane type resin, crosslinking can be performed by heating thepolyurethane type resin after being applied to the polyvinyl chloridetype resin film (a). This heat crosslinking may be carried out uponbonding of the metal layer or in advance. On this occasion, the heatcrosslinking may be performed by heating generally at about 100 to about200° C. for about 0.5 to about 30 hours.

The polyurethane type resin layer (b) formed as described above isselected so as to have a total visible light transmission of at least30%, preferably not lower than 40%, and more preferably not lower than40%, and most preferably not lower than 50%, and a tensile strength at100% elongation within the range of 50 to 550 kg/cm², preferably 60 to450 kg/cm², and more preferably 70 to 350 kg./cm².

Further, it is desirable that the polyurethane type resin layer (b) havea glass transition temperature (Tg) within the range of generally notlower than -60° C. preferably not lower than -50° C., and morepreferably not lower than -40° C., and a surface tension of not smallerthan 30 dyne/cm, preferably not smaller than 33 dyne/cm, and morepreferably not smaller than 35 dyne/cm in order to increase bondingbetween adjacent layers. It is also preferred that the resin layer (b)have a molecular structure crosslinked three-dimensionally whilemaintaining its flexibility so as to have thermal resistance and solventresistance.

Metal Layer (c)

On the surface of the aforementioned polyurethane type resin layer isbonded the metal layer (c) in order to impact the laminated resin filmof the present invention with a metallic tone appearance. The thicknessof the metal layer (c) may be within the range of 50 to 2,000 Å,preferably 100 to 1,000 Å and more preferably 300 to 600 Å.

As the method for bonding the metal layer of such a thickness on thepolyurethane type resin layer (b), there can be used a transfer methodin which the polyurethane type resin is coated on the polyvinyl chloridetype resin film, and before drying a deposited film composed of apolyester film on which a metal is deposited (the deposited layer peelsoff from the polyester film with ease) is laminated on the polyurethanetype resin layer in such a manner that the metal-deposited surfacecontacts the polyurethane type resin, followed by peeling off only thepolyester film, or alternatively, a polyurethane type resin solution iscoated on the metal-deposited surface of a deposited film composed of apolyester film having deposited thereon a metal deposited film, dried,and a polyvinyl chloride type resin solution is coated thereon anddried, followed by peeling off the polyester film; or a plasma method inwhich raw material gas is converted into a plasma state to produceexcited molecules, atoms, ions, radicals which are chemically veryactive to promote chemical reaction to prepare a thin film on asubstrate. Generally, metal deposition method and sputtering method aresuitable.

Bonding of the metal layer onto the polyurethane type resin layer (b) bymetal deposition or sputtering can be carried out by a method know perse, for example, by methods as described in Vacuum Deposition (authoredby Siegfried-Schiller, Ulrich, and Heisich, translated by Japan VacuumTechnology Co., Ltd., and other literatures.

No particular limitation is posed on the kind of the metal used forforming the metal layer (c) and can be selected from a wide rangedepending on the utility of the laminated resin film. There can becited, for example, aluminum, gold, silver, copper, nickel, chromium,magnesium, zinc, etc., or alloys composed of two or more of them. Amongthem, aluminum, chromium, nickel, etc. are preferred from a point ofview of workability, ease of formation, durability and the like whilechromium is particularly preferred in view of corrosion resistance.

Acrylic Type Resin Layer (d)

While the laminated resin film of the present invention may comprise theaforementioned polyvinyl chloride type resin film (a), polyurethane typeresin layer (b), metal layer (c), an acrylic type resin layer (d) mayalso be provided as an additional layer on the metal layer (c). Thisprevents corrosion of the metal layer due to penetration of moisturefrom the back surface (the surface other than the side of the polyvinylchloride type resin film (a) and the polyurethane type resin (b), andalso prevents transfer deterioration of the metal layer toward thepolyurethane type resin by bonding and fixing the acrylic type resinlayer (d) to the metal layer, thus making it possible to improve variousphysical properties such as weatherability, etc.

The acrylic type resin which can be used for this purpose includespolymers at least 50% by weight, preferably 55 to 98% by weight, andmore preferably 60 to 95% by weight, based on total polymer, of(meth)acrylic type monomer units.

As the (meth)acrylic type monomer used in the preparation of suchacrylic type resins, there can be cited, for example, (meth)acrylic typemonomers, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl(meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl(meth)acrylate, octyl (meth)acrylate, propyl (meth)acrylate,2-hydroxyethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,2-hydroxypropyl (meth)acrylate, dimethylaminoethyl (meth)acrylate,glycidyl (meth)acrylate, and ethylene glycol dimethacrylate, etc., vinylester monomers such as vinyl acetate, and vinyl propionate, etc. Thesemay be used singly or two or more of them may be used in combination.

The acrylic type monomers may be copolymerized with at least one othercopolymerizable vinyl monomer. As for the vinyl monomer, there can becited, for example, carboxyl group-containing vinyl monomers such asacrylic acid, methacrylic acid, itaconic acid, etc., and hydroxylgroup-containing vinyl monomers such as hydroxymethyl ester,hydroxyethyl ester, hydroxypropyl ester, hydroxybutyl ester,hydroxypentyl ester, hydroxyhexyl ester, etc. of (meth)acrylic acid, andfurther epoxy group- and amino group-containing vinyl monomers.

As the components other than described above, there can be utilizedpolyvinyl chloride, vinyl chloride-vinyl acetate copolymers, urethaneresins, epoxy resins, vinyl chloride-ethylene copolymers, etc.

The acrylic type resin applied onto the metal (c) generally must have amoderate flexibility and strength, and desirably have a weight averagemolecular weight of 10,000 to 1,000,000, and preferably 50,000 to500,000. For the same reason, it is desirable that its Tg be -50° C. to70° C., preferably -30° C. to 50° C., and more preferably -10° C. to 30°C.

Application of such an acrylic type resin onto the metal layer (c) canbe carried out, for example, by preparing a solution or dispersion ofthe acrylic type resin having a suitable viscosity, and applying thesolution or dispersion by spray coating, curtain flow coating, rollcoater coating, doctor knife coating, dip coating, flow coating, brushcoating, or the like.

In this case, the acrylic type resin may be crosslinked utilizingfunctional groups such as hydroxyl groups which exist therein, or may beblended with colorants (dyes, general pigments, pearl pigments, metalflakes, etc.), ultraviolet light absorbent, stabilizers, resins formodification according to the circumstances.

The thickness of the acrylic type resin layer (d) is not limitedstrictly but is suitably within the range of generally 0.5 to 100microns, preferably 0.7 to 30 microns, and more preferably 1 to 15microns.

In the present invention, a layer composed of a resin such as theaforementioned polyurethane type resin or the like, instead of theacrylic type resin layer (d), may be provided on the metal layer (c).

Utility

The laminated resin film provided by the present invention can be usedas a marking film, as described above, by being affixed onto a suitablesubstrate for imparting it with a beautiful, metallic tone ornament.

For the purpose, a layer of an adhesive or pressure-sensitive adhesivemay be applied on the surface of the metal layer (c) or acrylic typeresin layer (d) of the laminated resin film of the present invention,and further, a release paper may be affixed onto the layer so that thelayer can be protected from contamination or the like until time of use.

The adhesive or pressure-sensitive adhesive which can be applied is notlimited particularly and may be selected suitably depending on the kindof substrate onto which it is to be affixed. Generally, those excellentin water resistance are preferred. There can be cited, for example,rubber type adhesives, acrylic adhesives, vinyl acetate type adhesives,urethane type adhesives, silicone type adhesives, and other types ofadhesives as well as suitable mixed type adhesives thereof.

As the aforementioned rubber type adhesive, there can be cited, forexample, natural rubbers, isoprene rubbers, styrene-butadiene rubbers,styrene-butadiene blocked copolymers, styrene-isoprene blockedcopolymers, butyl rubbers, polyisobutylenes, silicone rubbers, polyvinylisobutyl ethers, chloroprene rubbers, nitrile rubbers, etc., andmixtures thereof or those containing at least one of them as the majorcomponent. Those having some crosslinked structures between themolecules may be used preferably.

The acrylic type adhesive and vinyl acetate type adhesive may be, forexample, an adhesive layer formed of a solvent type adhesive composedmainly of an unsaturated carboxylic acid ester type copolymer, andparticularly preferred is an adhesive layer formed of 100 parts byweight of a solvent type adhesive derived from 99.9 to 85 parts byweight of an unsaturated carboxylic ester monomer and 0.1 to 15 parts byweight of a vinyl monomer having a crosslinking functional group andhaving a glass transition temperature (Tg) of no higher than -20° C.; 70to 400 parts by weight of a detergent; and 0.01 to 20 parts by weight ofa crosslinking agent which can crosslink with the aforementionedcrosslinking functional group.

As the unsaturated carboxylic acid ester monomer for preparing thecopolymer constituting the aforementioned adhesive, there can be cited,for example, (meth)acrylic acid ester monomers such as methyl(meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl(meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl(meth)acrylate, octyl (meth)acrylate, etc., and vinyl ester monomerssuch as vinyl acetate, vinyl propionate, etc.

As the vinyl monomer having a crosslinking functional group forobtaining the aforementioned polymers, there can be cited, for example,carboxyl group-containing vinyl monomers such as acrylic acid,methacrylic acid, itaconic acid, etc., and hydroxyl group-containingvinyl monomers such as hydroxymethyl ester, hydroxyethyl ester,hydroxypropyl ester, hydroxybutyl ester, hydroxypentyl ester,hydroxyhexyl ester, etc. of acrylic acid, hydroxymethyl ester,hydroxyethyl ester, hydroxypropyl ester, hydroxybutyl ester,hydroxypentyl ester, hydroxyhexyl ester, etc. of methacrylic acid, andfurther epoxy group and amino group-containing vinyl monomers.

As the solvent, ethyl acetate, toluene, acetone, isopropyl alcohol, etc.are preferred.

As the crosslinking agent, there can be cited organic multifunctionalisocyanate compounds. Specific examples thereof include so-calledaromatic multifunctional isocyanates such as p-phenylene diisocyanate,4,4'-diphenylmethane diisocyanate, 2,4-toluylene diisocyanate,2,6-toluylene diisocyanate, xylylene diisocyanate, triisocyanate,naphthalene 1,5-diisocyanate, etc., pentamethylene diisocyanate,hexamethylene diisocyanate, cyanate, heptamethylene diisocyanate,4,4'-dicyclohexylbutane diisocyanate, etc.

The glass transition temperatures, Tg, of the aforementioned copolymerswere measured by the following measurement method.

About 10 mg of a resin solution sample is weighted in a cell and driedat 100° C. for 2 hours, which is used as a sample for measurement. UsingDifferential Scanning Calorimeter Model DT-30, produced by ShimazuSeisakusho, measurement and determination are made at a temperatureelevation rate of 20° C./min starting from -80° C. The measurement iscarried out using nitrogen gas as a carrier gas at a flow rate of 20cc/min.

Examples of the aforementioned urethane type adhesive include thosecomposed of high molecular weight compounds produced by the reaction ofan isocyanate, such as triphenylmethane-p,p',p"-triisocyanate,hexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate, toluenediisocyanate, or the like, with a compound having an activated hydrogenatom, for example, polyester, polyether glycol, polyacrylate, orpolyamide having an activated hydrogen atom, their mixtures or thosecontaining at least one of them as a major component.

As the silicone type adhesive, there can be cited linear or graftedcompounds containing as a major component dimethylpolysiloxane,diphenylpolysiloxane, or organopolysiloxane.

These may be applied onto the laminated resin film, for example, byforming a layer of the aforementioned adhesive on a release paperobtained by treating with silicone a polyethylene layer of a highquality paper laminated on the surfaces thereof with a polyethylene,polypropylene film treated with silicone, polyethylene film treated withsilicone, or the like, and laminating thereon the laminated resin film.

The laminated resin film of the present invention can be affixed onto asurface of a substrate by a hot lamination method. For example,

i) In the Case Where There is the Acrylic Resin Layer (d)

At a softening temperature of the acrylic resin layer (d), the laminatedresin film is pressed onto the adherend at a pressure of 1 to 50 kg/cm²using a rubber roll or the like. In a particular case where the adherendis aluminum, it is preferable that the surface thereof is subjected toformation treatment in advance to form an oxide film because thisincreases the degree of adhesion;

ii) In the Case Where the Acrylic Resin Layer (d) is Absent

A resin substrate which gets softened with heating is used as anadherend, and a metal substrate coated on its surface with such a resinis also used. The laminated film is pressed onto the substrate at thesoftening temperature of the resin at a pressure of 1 t 50 kg/cm² usinga rubber roll or the like.

The laminated resin film of the present invention allows printing on itssurface layer (polyvinyl chloride layer) freely as desired, and canprovide various designs. Further, the use of inks having excellentweatherabilities (for example, Haiesu SP Ink, Haiesu FP Ink, etc.produced by Nippon Carbide Industry) enables their use in the open airand can provide a film having a flexibility and having a metallicappearance which has never been obtained conventionally.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic, fragmental cross-sectional view showing alaminated resin film having a metallic appearance according to Examples1 to 5; and

FIG. 2 is a schematic, fragmental cross-sectional view showing alaminated resin film having a metallic appearance according to Examples6 and 7.

BEST MODE FOR CARRYING OUT THE INVENTION EXAMPLE

Next, the present invention will be explained more concretely by way ofexamples.

The physical and chemical properties described in the descriptionincluding examples and in claims have been measured by the methodsdescribed below.

(1) Tensile Testing (Measurement of Tensile Strength at 5% Elongation)

Samples for tensile testing were prepared by cutting sample films topredetermined shape according to JIS-K-6734, and the samples weresubjected to tensile testing using a tensile tester (produced by ToyoSeiki Seiksakusho Co., Ltd.) under the conditions of a temperature of23°±2° C., in an atmosphere of a relative humidity of 50±5%, anelongation rate of 200 mm/min., an elongation distance of 100 mm, and achart speed o 500 mm/min. From the chart obtained then strengths at 5%elongation were read, and the values were defined as tensile strengthsat 5% elongation.

(2) Tensile Testing (Measurement of Tensile Strength at 100% Elongation)

According to JIS-K-6734 in which it is prescribed that a film of theresin for the polyurethane layer is formed on a glass plate and dried ina drier at 120° C. ×1 Hr and films having a thickness of 10μ are sued assamples, sample films were cut to a determined shape to prepare samplesfor tensile testing. The samples were subjected to tensile using atensile tester (produced by Toyo Seiki Seisakusho Co., Ltd.) under theconditions of a temperature of 23°±2° C., in an atmosphere of a relativehumidity of 50±5%, an elongation rate of 200 mm/min., an elongationdistance of 100 mm, and a chart speed o 100 mm/min. From the chartobtained then strengths at 100% elongation were read.

(3) Total Light Transmission

Total light transmission was measured using a direct reading Haze Meter(produced by Toyo Seiki Seisakusho Co., Ltd.) according to themeasurement of light transmission prescribed in JIS-K-6714.

(4) Heat Resistance of Polyurethane Resin Layer

The same samples as in Tensile Testing (2) above were prepared and thesamples were mounted on an alkyd melamine coated white panel (producedby Nippon Test Panel Co., Ltd.; hereafter, simply referred to as whitepanel) and measured as follows.

That is, using Macbeth Spectrometer Color-Eye MS-2020 (produced byKollomorgen Corporation) as a tester measurement was performed and dEvalues according to CIE 1976 (L*a*b*) under standard light source C wereobtained for standard samples and heat-treated samples (treated at 150°C. for 20 minutes), and the numerical values obtained were evaluated bythe following five ratings:

5: Below 3

4: 3 or more and below 5

3: 5 or more and below 7

2: 7 or more and below 9

1: 9 or more

(5) Heat Resistance

A metallic tone film was cut to 50 mm×50 mm, and the peel paper waspeeled off. Thereafter, this was affixed onto an alkyd melamine coatedpanel (produced by Nippon Test Panel Industry Co., Ltd.) using asqueegee. Then, this was left to stand in an oven with internal aircirculation set at 80° C.±2° C. for 168 hours without movement to carryout heat treatment. After completion of the heat treatment, the panelwas taken out and the state of the film crack was observed and rated inthe following five ratings:

5: Film surface has no crack and has a mirror surface property.

4: Film surface has cracks partly but retains a mirror surface property.

3: Film surface has cracks partly and has lost a mirror surface propertypartly.

2: Film surface has cracks over its entirety and has lost a mirrorsurface property partly.

1: Film surface has cracks over its entirety and has lost a mirrorsurface.

(6) Curved Surface Affixing Suitability

Metallic tone films were affixed onto a curved surface on the bottom ofa stainless steel bowl of 180 mm in diameter and evaluation was made bydetermining the diameter of the circular metallic tone film for exterioruse which was able to be affixed without causing wrinkles. Evaluationmethod was to find out maximum diameter value, which was defined ascurved surface affixing suitability value, and evaluated by thefollowing five ratings:

5: 40 mm or larger

4: 30 mm of larger and smaller than 40 mm

3: 20 mm or larger and smaller than 30 mm

2: 10 mm or larger and smaller than 20 mm

1: Smaller than 10 mm

(7) Degree of Adhesion of Polyurethane Type Resin Layer onto PolyvinylChloride Resin Film

A film prior to the stage of metal deposition was formed with apressure-sensitive adhesive layer, and the film was affixed onto analuminum plate. The plate was immersed in hot water at 80° C. for 4hours and then taken out from the hot water, left to stand for 24 hours.Thereafter, the degree of adhesion between the surface resin layer andthe (first) intermediate layer was checked by trying to separate thelayers with a single blade razor.

Evaluation was made by the following five ratings:

5 Surface resin layer and (first) intermediate layer are bondedcompletely.

4: Surface resin layer and (first) intermediate layer are separated by20% or less.

3: Surface resin layer and (first) intermediate layer are separated byabove 20% and 50% or less.

2: Surface resin layer and (first) intermediate layer are separated byabove 50% and 80% or less.

1: Surface resin layer and (first) intermediate layer are separated byabove 80%.

(8) Degree of Adhesion of Metal Layer

A cellophane tape was pressed onto the metal layer side of samples priorto the sage of forming a pressure-sensitive adhesive layer (or adhesivelayer) or second intermediate layer, and the state of peeling of themetal layer when the cellophane tape was peeled off quickly was observedand evaluated by the following five ratings:

5: Metal layer does not peel off.

4: Metal layer peels off in dots.

3: Metal layer peels off by 20% or less.

2: Metal layer peels off by above 20% and 80% or less

1: Metal layer peels off by above 80%.

(9) Hot Water Resistance (1)

Films prior to metal deposition were immersed in hot water at 40° C. for168 hours, and their degree of whitening was evaluated by the followingfive ratings:

5 No abnormality.

4: Very slight whitening occurs in a part of the film.

3: Very slight whitening occurs over the entire film.

2: Whitening occurs in a part of the film.

1: Whitening occurs over the entire film.

(10) Hot Water Resistance (2)

A metallic tone film was cut to 50 mm×50 mm, and the peel paper waspeeled off. Thereafter, this was affixed onto an alkyd melamine coatedpanel (produced by Nippon Test Panel Industry Co., Ltd.) using asqueegee. After being left to stand at room temperature for 72 hours,the panel was immersed in hot water at 80° C. for 4 hours, andevaluation was made by the same criteria as above.

(11) Solvent Resistance

(1) Against gasoline: A metallic tone film was cut to 50 mm×50 mm, andthe peel paper was peeled off. Thereafter, this was affixed onto analkyd melamine coated panel (produced b Nippon Test Panel Industry Co.,Ltd.) using a squeegee. After being left to stand at room temperaturefor 72 hours, the panel was immersed in gasoline at 20° C. for 30minutes, and the appearance of the film at that time was evaluated bythe following five ratings:

5: No abnormality.

4: Cracks occur in 20% or less of the entire film surface

3: Cracks occur in 50% or less of the entire film surface

2: Cracks occur in 80% or less of the entire film surface

1: Cracks occur over the entire film surface.

(2) Against Methanol: A metallic tone film was cut to 50 mm×50 mm, andthe peel paper was peeled off. Thereafter, this was affixed onto analkyd melamine coated panel (produced by Nippon Test Panel Industry Co.,Ltd.) using a squeegee. After being left to stand at room temperaturefor 72 hours, the panel was immersed in methanol at 20° C. for 10minutes, and the appearance of the film at that time was evaluated bythe following five ratings:

5: No abnormality.

4: Surface mirror property is lost from place to place in the edgeportion of the film. is lost only in the

3: Surface mirror property edge portion of the film.

2: Surface mirror property is lost partly including the edge portion ofthe film.

1: Surface mirror property is lost over the entire film surface.

(12) Chemical Resistance

(1) Against Acid: A metallic tone film was cut to 50 mm×50 mm, and thepeel paper was peeled off. Thereafter, this was affixed onto an alkydmelamine coated panel (produced by Nippon Test Panel Industry Co., Ltd.)using a squeegee. After being left to stand at room temperature for 72hours, the panel was immersed in an aqueous solution of 200 ppm H₂ SO₃at room temperature for 14 days, and the appearance of the film at thattime was evaluated by the following five ratings:

5: No abnormality.

4: Corrosion of metal occurs from place to place in the edge portion ofthe film.

3: Corrosion of metal occurs only in the edge portion of the film.

2: Corrosion of metal occurs partly including the edge portion of thefilm.

1: Corrosion of metal occurs over the entire film surface.

(2) Against Brine: A metallic tone film was cut to 50 mm×50 mm, and thepeel paper was peeled off. Thereafter, this was affixed onto an alkydmelamine coated panel (produced by Nippon Test Panel Industry Co., Ltd.)using a squeegee. After being left to stand at room temperature for 72hours, the panel was immersed in an aqueous solution of 3% NaCl at roomtemperature for 1 month, and the appearance of the film at that time wasevaluated by the same five ratings as in the acid resistance evaluation(1) above.

(13) Weatherability

Weatherability (1): A metallic tone film was cut to 35 mm×60 mm, and thepeel paper was peeled off. Thereafter, this was affixed onto an alkydmelamine coated panel (produced by Nippon Test Panel Industry Co., Ltd.)using a squeegee. The panel was set at an angle of 5° facing the southin Florida, U.S.A. After being exposed in the open air for 6 months or12 months the appearance of the film was visually evaluated by thefollowing five ratings:

5: No abnormality.

4: Surface mirror property is lost from place to place in the edgeportion of the film.

3: Surface mirror property is lost only in the edge portion of the film.

2: Surface mirror property is lost partly including the edge portion ofthe film.

1: Surface mirror property is lost over the entire film surface.

Weatherability (2): A metallic tone film for exterior use was affixedonto an aluminum panel (17×35 mm), and left to stand at room temperaturesufficiently. Thereafter, the plate was subjected to acceleratedexposure test using Q.U.V. (The Q-Panel Company).

The exposure conditions at that time were UV light irradiation at ablack panel temperature 60° C. for 8 hours, and moisture condensation ata black panel temperature of 60° C., which formed one cycle.

Evaluations were made by comparing the samples with standard samples(surface resin layer) after 100 hours, 300 hours, and 7 hours,respectively, by the same evaluation criteria as in the aboveweatherability (1).

Weatherability (3): Almost the same as the above weatherability (2)except that the exposure conditions were changed to black paneltemperature of 70° C.

EXAMPLE 1

First, a film of 40μ in thickness was prepared by a casting method usinga resin composition composed of the following basic formulation, andthis was used as a polyvinyl chloride type resin film in a laminatedresin film having a metallic tone appearance.

The film had a tensile strength at 5% elongation of 1.5 kg/cm and atotal light transmission of 89%. As indicated later on, the film wassubjected to the subsequent steps in a state of being bonded onto asupport film.

    ______________________________________                                        Base Formulation                                                              ______________________________________                                        Vinyl chloride resin  100                                                     Ethylene/vinyl ester type resin                                                                     25                                                      Polyester plasticizer 10                                                      ______________________________________                                    

Nikavinyl SG-1100N (produced by Nippon Carbide Industry Co., Ltd.) andElvalloy were used as the vinyl chloride resin and the ethylene/vinylester type resin, respectively. As the polyester plasticizer, there wasused one synthesized from a mixed dihydric alcohol composed of propyleneglycol, butanediol and hexanediol, and adipic acid and having a numberaverage molecular weight (Mn) of about 3,000. Specifically, thepreparation of the film by the casting method was performed as follows.

That is, Tetrahydrofuran was added to mixed resin components so that theconcentration of the resin was 20% by weight, and mixture was stirredfor dissolution at 100° C. for 2 hours in a sealed vessel to obtain aresin solution composition.

Then, after being cooled and defoamed, the aforementioned resin solutioncomposition was cast on a polyester film (support film) using a caster,dried with hot air at 140° C. for 15 minutes to prepare a polyvinylchloride type resin film in a state of being bonded onto the supportfilm.

Next, the polyurethane (urethane resin) solution described below wascoated on one surface of the aforementioned polyvinyl chloride typeresin film using a screen printer (trade name: Minomat 600L, produced byMino Group) and a 180 mesh monotetrone screen, and dried in an ovencontrolled at 120° C.±3° C. for 60 minutes to form a 10μ thickintermediate layer. The intermediate layer had a total lighttransmission of 88%. As the polyurethane solution, there was used tradename: Barnok L7-920 (produced by Dainippon Ink and Chemical IndustryCo., Ltd., 25±1% nonvolatile content, solvent toluene,secondary-butanol, viscosity Z₁ -Z₄).

After a metal layer having a thickness of about 500Å was formed byaluminum deposition on a surface of the aforementioned polyurethaneresin layer, a mixed solution composed of 100 parts by weight of anacrylic type pressure-sensitive adhesive (trade name: PE-121, producedby Nippon Carbide Industry Co., Ltd.)) and 1 part by weight of acrosslinking agent (trade name: Coronate L, produced by NipponPolyurethane Industry Co., Ltd.) was coated on the surface of the metal,and dried to form a pressure-sensitive adhesive layer of about 35μthick. Further, after a silicone-coated release paper was affixed ontothe coated surface of the pressure-sensitive adhesive layer, the supportfilm composed of a polyester was peeled off to prepare a laminated resinfilm having a metallic appearance.

The film thus prepared, as schematically shown in fragmentalcross-section in FIG. 1, has a structure composed of a polyvinylchloride type resin film 1 having thereon a coating of a polyurethanetype resin layer 2a having laminated thereon a metal layer (d), (a metallayer 3) a pressure-sensitive adhesive layer 5, and a release paper 6 inthis order.

Results of evaluations of the aforementioned test items on the laminatedresin film having a metallic appearance according to Example 1 togetherwith the results in Examples 2 to 7 are shown in Table 1 below.

For comparison, results in the case of the surface resin layer alone(Comparative Example 1 explained below) are also shown.

EXAMPLE 2

The laminated resin film having a metallic appearance according toExample 2 had substantially the same structure and size as that inExample 1 and prepared by substantially the same method as Example 1above except that the polyurethane type resin layer was made of theurethane type resin described below.

The polyurethane resin in Example 2 is a graft polymer obtained bygrafting the polyurethane resin below with an acrylic monomer, that is,a non-discoloring acryl grafted urethane lacquer, trade name: BarnokL8-921 (produced by Dainippon Ink and Chemicals Industry Co., Ltd.,nonvolatile content: 25±1%, solvent toluene, DMF) obtained by grafting amixed monomer containing at least a hydroxyl group-containing α-βethylene type monomer and a carboxyl group-containing α-β ethylene typemonomer to a base urethane, trade name: Barnok L7-920 used in ReferenceExample 1. The layer made of the aforementioned urethane type resin hada total light transmission of 88%.

EXAMPLE 3

The laminated resin film having a metallic appearance according toExample 3 had substantially the same structure and size as that inExample 1 and prepared by substantially the same method as Example 1above except that the polyurethane type resin layer was made of theurethane type resin described below.

The urethane type resin in Example 3 has a basic formulation composed of100 parts by weight of a urethane resin and 25 parts by weight acrosslinking agent. As the aforementioned urethane resin, there was usedtrade name: Barnok K7-920, and as the crosslinking agent was usedbutylated melamine resin, trade name: Super Backamine J-820-60 (producedby Dainippon Ink and Chemicals Industry Co., Ltd., nonvolatile content60%, solvent xylene, n-butanol, viscosity Q-T). The layer made of theaforementioned urethane type resin had a total light transmission of88%.

EXAMPLE 4

The laminated resin film having a metallic appearance according toExample 4 had substantially the same structure and size as that inExample 1 and prepared by substantially the same method as Example 1above except that the polyurethane type resin layer was made of theurethane type resin described below.

The urethane type resin in Example 4 has a basic formulation composed of100 parts by weight of a grafted polyurethane resin and 25 parts byweight a crosslinking agent. As the aforementioned grafted polyurethaneresin, there was used trade name: Barnok L8-971 used in ReferenceExample 2 above, and as the crosslinking agent was used the butylatedmelamine resin, trade name: Super Beckamine J-820-60 used in ReferenceExample 3 above. The layer made of the aforementioned urethane typeresin had a total light transmission of 88%.

EXAMPLE 5

The laminated resin film having a metallic appearance according toExample 5 had substantially the same structure and size as that inExample 4 and prepared by substantially the same method as Example 4above except that the polyurethane type resin layer was made of theurethane type resin described below.

The urethane type resin in Example 5 was prepared by first mixing apolyester diol (prepared by mixing in total 100 parts by weight ofadipic acid:maleic anhydride:propylene glycol:ethyleneglycol=100:1:50:55) with 250 parts by weight of a mixed solvent composedof dimethylformamide:methyl ethyl ketone:=3:1 and stirring the mixturein a polymerization apparatus at 80° C. for 4 hours for polymerization)with hexamethylene diisocyanate in a ratio of 5:2, and stirring themixture in a polymerization apparatus at 80° C. for 6 hours. Further,100 parts by weight of the aforementioned polyurethane resin was mixedwith 10 parts by weight of hydroxypropyl methacrylate, 5 parts by weightof acrylic acid, 2 parts by weight of methyl acrylate, and 30 parts byweight of azobisisobutyronitrile, and stirred in a polymerizationapparatus at 80° C. for 3 hours. The layer made of the aforementionedurethane type resin had a total light transmission of 88%.

EXAMPLE 6

The laminated resin film having a metallic appearance according toExample 6 is composed of the metallic tone film of Example 4 above inwhich an acrylic type resin layer (d) is formed by bonding onto theopposite surface of the metal layer (c) for backing it. The film thusprepared, as schematically shown in fragmental cross-section in FIG. 2,has the common structure as the metallic tone film for exterior use asshown in FIG. 1 except that the aforementioned acrylic type resin layer(d) 4 is formed by bonding onto the opposite surface of the metal layer(c) (metal layer 3). The polyurethane resin layer 2a in FIG. 1corresponds to the polyurethane type resin layer 2 in FIG. 2.

After the acrylic type resin layer 4 was formed with the metal layer 3in the same manner as in Example 4 above, the polymer solutioncontaining an acrylic type resin described below was coated on theopposite surface of the aforementioned metal layer using a screenprinter (trade name: Minomat 600 L, produced by Mino Group) and a 180mesh monotetrone screen in the same manner as the layer in Example 1above. Then it was dried in an oven controlled at 120° C.±3° C. for 60minutes to form a 10μ thick intermediate layer. The aforementionedacrylic type resin layer had a total light transmission of 88%.

The polymer solution for forming the aforementioned acrylic type resinlayer 4 was prepared by adding 14 parts by weight of Coronate EH(produced by Nippon Polyurethane Industry Co., Ltd.) to 100 parts byweight of a xylene solution composed of 58% by weight of methylmethacrylate, 30% by weight of butyl acrylate and 12% by weight of2-hydroxyethyl methacrylate and having a resin content of 48%, stirringsufficiently for mixing.

Degree of adhesion between the metal layer 3 and the acrylic type resinlayer 4 was evaluated by the same method described in the column of"Degree of Adhesion of Polyurethane Type Resin Layer to Surface ResinLayer" to reveal that degree of adhesion was very good.

EXAMPLE 7

The laminated resin film having a metallic appearance according toExample 7 had substantially the same structure and size as that inExample 6 and prepared by substantially the same method as Example 6above except that the polyurethane type resin layer was made of theurethane type resin used in Example 5 above.

COMPARATIVE EXAMPLE 1

The laminated resin film having a metallic appearance according toComparative Example 1 was prepared in the same manner as in Example 1above except that the metal layer (d) (metal layer 3) was formed bybonding to the polyvinyl chloride type resin film 1 directly withoutforming the polyurethane type resin layer 2a.

                                      TABLE 1                                     __________________________________________________________________________                                                   Comparative                                Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                        Item of Testing                                                                           1    2    3    4    5    6    7    1                              __________________________________________________________________________    Tensile strength at 5%                                                                    1.5  1.5  1.5  1.5  1.5  1.8  1.8  1.5                            elongation (kg/cm)                                                            Tensile strength at                                                                       100  170  140  200  200  200  200  --                             100% elongation of                                                            polyurethane type resin                                                       layer (kg/cm)                                                                 Total light transmission                                                                  88   88   88   88   88   88   88   --                             of polyurethane type                                                          resin layer (%)                                                               Hot water   3    3    4    5    5    5    5    1                              resistance (1)                                                                Hot water   3    2    4    5    5    5    5    1                              resistance (2)                                                                Degree of adhesion of                                                                     5    5    5    5    5    5    5    --                             polyurethane type resin                                                       layer to polyvinyl                                                            chloride type resin film                                                      Degree of adhesion                                                                        3    5    3    5    5    5    5    1                              of metal layer                                                                Curved surface affixing                                                                   5    5    5    5    5    5    5    5                              suitability (mm)                                                              Heat resistance                                                                           5    3    4    4    5    5    5    1                              (80° C. × 168 hr)                                                Gasoline Resistance                                                                       4    4    5    5    5    5    5    --                             (30 minutes)                                                                  Methanol Resistance                                                                       4    5    5    5    5    5    5    1                              (10 minutes)                                                                  Acid resistance                                                                           3    5    5    5    5    5    5    1                              (H2SO3 solution)                                                              Brine resistance                                                                          5    5    5    5    5    5    5    1                              (NaCl solution)                                                               Weatherability (1)                                                            Florida actual  6 months                                                                  3    3    4    5    5    5    5    1                              exposure test 12 months                                                                   3    3    3    4    4    5    5    1                              Weatherability (2)                                                            QUV 100 hr  4    4    5    5    5    5    5    1                                  300 hr  3    3    4    5    5    5    5    1                                  700 hr  3    3    3    4    4    5    5    1                              Weatherability (3)                                                            QUV 100 hr  2    2    2    5    5    5    5    1                                  300 hr  2    2    2    3    3    5    5    1                                  700 hr  2    2    2    3    3    5    5    1                              __________________________________________________________________________

From Table 1 above, it can be understood that the laminated resin filmshaving a metallic appearance according to Examples 1 to 5 are superiorover the laminated resin film having a metallic appearance according toComparative Example 1 in various properties, and the laminated resinfilms having a metallic appearance according to Examples 6 and 7 aremuch superior thereover in various properties.

INDUSTRIAL APPLICABILITY

The laminated resin film of the present invention is excellent inadhesion between various layers thereof, suffers no corrosion ordeterioration of the metal layer, has a sufficient weatherability whenused for exterior use, is flexible enough to be affixed onto curvedsurfaces, and is excellent in solvent resistance, hot water resistance,chemical resistance and the like; it is useful as a marking film forvehicles such as cars, trams, and motor cycles, as a braids for cars andthe like, as a marking film for signboards, outdoor advertisement towerand the like, and as an ornamental film for buildings, houses and thelike.

What we claim is:
 1. A laminated resin film having a metallicappearance, comprising:(a) a polyvinyl chloride resin film having atotal light transmission of at least 30% and a tensile strength at 5%elongation of not higher than 2 kg/cm; (b) a thin polyurethane resinlayer laminated on one surface of said resin film and having a totallight transmission of at least 30% and a tensile strength at 100%elongation within the range of 50 to 550 kg/cm; and (c) a metal layerhaving a thickness of 50 to 2,000 Å formed and adhering onto saidpolyurethane resin layer.
 2. The laminated resin film as claimed inclaim 1, wherein said polyvinyl chloride resin film (a) has a totallight transmission of no lower than 40%.
 3. The laminated resin film asclaimed in claim 1, wherein said polyvinyl chloride resin film (a) has atensile strength at 5% elongation within the range of 1.9 to 0.2 kg/cm.4. The laminated resin film as claimed in claim 1, wherein saidpolyvinyl chloride resin film (a) has a thickness within the range of 20to 200 microns.
 5. The laminated resin film as claimed in claim 1,wherein said polyurethane resin film (b) has a total light transmissionof no lower than 40%.
 6. The laminated resin film as claimed in claim 1,wherein said polyurethane resin film (b) has a tensile strength at 100%elongation within the range of 60 to 450 kg/cm².
 7. The laminated resinfilm as claimed in claim 1, wherein said polyurethane resin film (b) hasa thickness within the range of 0.5 to 100 microns.
 8. The laminatedresin film as claimed in claim 1, wherein said polyurethane resin film(b) is formed of a polyurethane resin having a glass transitiontemperature, Tg, of no lower than -60° C.
 9. The laminated resin film asclaimed in claim 1, wherein said polyurethane resin film (b) comprises ablend of:a crosslinking grafted polyurethane resin, and an amino resincrosslinking agent, said crosslinking graft polyurethane resin beingprepared by graft polymerizing a vinyl monomer mixture containing: ahydroxy group-containing vinyl monomer, and a carboxyl group-containingvinyl monomer, to a polyurethane resin, said polyurethane resin beingprepared using as a polyol component an ethylenically unsaturatedbond-containing polyester diol synthesized using a polycarboxylic acidhaving an ethylenically unsaturated bond as a part of a carboxylic acidcomponent, and containing on average 0.2 to 3 ethylenically unsaturatedbonds in the molecule and having a weight average molecular weightwithin the range of 300 to 200,000, said blend being heated andcrosslinked.
 10. The laminated resin film as claimed in claim 1, whereinsaid metal layer (c) is one formed by deposition or sputtering.
 11. Amarking film comprising the laminated resin film as claimed in claim 1.12. The laminated resin film as claimed in claim 1, wherein saidpolyvinyl chloride resin film (a) has a total light transmission of nolower than 50%.
 13. The laminated resin film as claimed in claim 1,wherein said polyvinyl chloride resin film (a) has a tensile strength at5% elongation within the range of 1.8 to 0.4 kg/cm.
 14. The laminatedresin film as claimed in claim 1, wherein said polyvinyl chloride resinfilm (a) has a thickness within the range of 25 to 170 microns.
 15. Thelaminated resin film as claimed in claim 1, wherein said polyvinylchloride resin contains 0 to 30% by weight of a copolymerizationcomponent.
 16. The laminated resin film as claimed in claim 1, whereinsaid polyurethane resin film (b) has a total light transmission of nolower than 50%.
 17. The laminated resin film as claimed in claim 1,wherein said polyurethane resin film (b) has a tensile strength at 100%elongation within the range of 70 to 350 kg/cm².
 18. The laminated resinfilm as claimed in claim 1, wherein said polyurethane resin film (b) hasa thickness within the range of 1 to 30 microns.
 19. The laminated resinfilm as claimed in claim 1, wherein said polyurethane resin film (b) isformed of a polyurethane resin having a glass transition temperature,Tg, of no lower than -50° C.
 20. The laminated resin film as claimed inclaim 1, wherein said polyvinyl chloride resin film (a) is a filmcomposed of a semi-hard polyvinyl chloride resin composition.
 21. Thelaminated resin film as claimed in claim 20, wherein said semi-hardpolyvinyl chloride resin composition comprises:(A) 100 parts by weightof a polyvinyl chloride which contains 0 to 20% weight of acopolymerization component; (B) 1 to 20 parts by weight of a liquidpolyester plasticizer having a number average molecular weight (Mn) offrom 1,500 to 6,000, and 0 to 10 parts by weight of another plasticizerfor polyvinyl chloride resins; and (C) 45 to 350 parts by weight of anethylene/vinyl ester of a saturated carboxylic acid/carbon monoxidecopolymer, based on total amount of said plasticizers (B), and has astress at yield within the range of 1 to 6 kg/cm².
 22. The laminatedresin film as claimed in claim 21, wherein the liquid polyesterplasticizer has a number average molecular weight (Mn) of 1,500 to4,000.
 23. The laminated resin film as claimed in claim 1, furthercomprising:(d) an acrylic resin layer on said metal layer of saidlaminated resin film.
 24. The laminated resin film as claimed in claim23, wherein said acrylic resin layer (d) has a thickness within therange of 0.5 to 100 microns.